CN109476971A - Acrylic pressure-sensitive adhesive compositions and use adhesive, polarizer adhesive and image display device made of it - Google Patents
Acrylic pressure-sensitive adhesive compositions and use adhesive, polarizer adhesive and image display device made of it Download PDFInfo
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- CN109476971A CN109476971A CN201780045281.4A CN201780045281A CN109476971A CN 109476971 A CN109476971 A CN 109476971A CN 201780045281 A CN201780045281 A CN 201780045281A CN 109476971 A CN109476971 A CN 109476971A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
- C09J133/04—Homopolymers or copolymers of esters
- C09J133/14—Homopolymers or copolymers of esters of esters containing halogen, nitrogen, sulfur or oxygen atoms in addition to the carboxy oxygen
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
- C09J11/02—Non-macromolecular additives
- C09J11/06—Non-macromolecular additives organic
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J133/00—Adhesives based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Adhesives based on derivatives of such polymers
-
- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/30—Polarising elements
-
- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F2202/00—Materials and properties
- G02F2202/28—Adhesive materials or arrangements
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Polarising Elements (AREA)
- Adhesive Tapes (AREA)
- Liquid Crystal (AREA)
- Surface Treatment Of Optical Elements (AREA)
Abstract
It provides: when manufacture liquid crystal display device; adhesive used in stickup as polarizer (protective film) and liquid crystal cells (glass) in use, it is available after embody excellent re-workability for a long time and if exposed to hot and humid environment in the case where will not cause damp and hot albefaction adhesive acrylic pressure-sensitive adhesive compositions.A kind of acrylic pressure-sensitive adhesive compositions, contain: acrylic resin (A)；With, in the structure respectively containing 1 or more reactive functional groups and the silane coupling agent (B) of alkoxy, acrylic resin (A) is the acrylic resin of 5~50 weight % of structural unit of at least one kind of polar functionalities monomer (a1) comprising being originated from hydroxyl monomer, carboxyl group-containing monomer, nitrogen containing monomer, and silane coupling agent (B) is 15 weight % oligomeric silane coupling agent (B1) below containing alkoxy group content.
Description
Technical field
It is bonded the present invention relates to acrylic pressure-sensitive adhesive compositions and using adhesive and polarizer made of it
Agent is further specifically related to: after embody for a long time excellent re-workability and can be formed not vulnerable to the influence of moisture,
It will not cause the acrylic pressure-sensitive adhesive compositions of the reduced adhesive of durability.
In the past, it will be covered by the two sides of the polarizing film of the formation such as the polyvinyl alcohol film that imparts polarizability with protective film
And polarizer is obtained, it is laminated on the surface for being clamped with the liquid crystal cells of the liquid crystal composition through being orientated between 2 glass plates, thus
Image display device can be manufactured.In order to be stacked in polarizing plate layer on the surface of the liquid crystal cells, it is usually carried out: will be arranged
It is connected to above-mentioned liquid crystal cells face in the adhesive phase of polarisation plate surface, and is squeezed, to carry out.
For being suitble to these protective films using comprising the bonding of polyvinyl alcohol resin with the bonding agent of polarizing plate sticking
Agent, specifically, aqueous solution made of compounding polyvinyl alcohol resin and crosslinking agent is coated on polarizing film and protection is laminated
It after film, is thermally dried, to manufacture polarizer.In the manufacturing process of above-mentioned polarizer, preferably contained in bonding agent
Moisture is suitble to the triacetate cellulose film (TAC film) for having used penetrability high as protective film through protective film so far,
But in recent years, from the viewpoint of dimensional stability, durability, olefin-based film, particularly cyclic olefine film are gradually used
(COP film) replaces protective film of the TAC film as polarizing film.
Adhesive used in stickup to such polarizer and liquid crystal cells (glass substrate) requires heat resistance, moisture-proof
Hot etc durability.Especially under hot and humid environment, there are the following problems: moisture immerses adhesive phase, with glass base
The cementability of plate can reduce, and polarizer from glass substrate portion floats or removes.In order to solve the problems, by viscous
Silane coupling agent is compounded in mixture, so as to realize in terms of the humidity resistance improve but compounding silane coupling agent in the case where,
Silane coupling agent slowly reacts, therefore there are problems that bonding force rises, long-term re-workability reduces.
In addition, use cyclic olefine film as in the case where the protective film of polarizer, if be exposed under hygrothermal environment,
When then there is recovery to room temperature, due to dew condensation phenomenon the problem of adhesive phase meeting albefaction (damp and hot albinism).
In addition, adhesive used in previous polarizer is used separately according to the type of polarizer, but in cost, operation
The aspect of property, seeks the adhesive that could be used that in the diverse situation of polarizer.
The adhesive excellent as such re-workability and wet-heat resisting albefaction, such as one is described in patent document 1
Kind adhesive composition, it includes: 100 parts by weight of adhesive resin (A)；It is 100~2000g/mol and alkane with, epoxide equivalent
Oxygroup content is 0.1~20 parts by weight of organosilan oxygroup oligomer (B) of 5~60 weight %, and aforementioned binder resin (A) is
Selected from as making acryl adhesive resin (A1), carbamate system adhesive obtained from the monomer polymerization without containing carboxyl
One or more of the group of resin (A2) and Polyester adhesive resin (A3) composition.
In addition, describing a kind of adhesive in patent document 2, in view of wet-heat resisting albefaction, use has been imported greatly
Measure the acrylic resin of polar functionalities monomer.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2016-44291 bulletin
Patent document 2: Japanese Unexamined Patent Publication 2013-213203 bulletin
Summary of the invention
Problems to be solved by the invention
However, (organosilan oxygroup is low for the silane coupling agent used about the adhesive recorded in above patent document 1
Polymers) functional equivalent and alkoxy group content are limited in a wide range and can use various silane coupling agents, but
There are rooms for improvement for the use of wet-heat resisting albefaction when the moisture permeabilitys such as cyclic olefine film low protective film.
In addition, on the other hand, it is contemplated that in the patent document 2 of wet-heat resisting albefaction, various optics structures can be used for by describing
The purport of part, but due to importing a large amount of polar functionalities monomers in acrylic resin, hydrophily becomes strong, uses work
When for the high TAC of the moisture permeability of protective film, acrylic film, the hydrolysis of silane coupling agent is promoted, exist it is long-term again plus
The problem of work reduces.
Therefore, in the present invention, in this context, a kind of acrylic pressure-sensitive adhesive compositions are provided, in manufacture liquid
When crystal device, adhesive used in the stickup as polarizer (protective film) and liquid crystal cells (glass) is in use, can
To obtain after embodying excellent re-workability for a long time, and if exposed to hot and humid environment in the case where will not cause
The adhesive of albinism.
The solution to the problem
Thus, the inventors of the present invention further investigate repeatedly in view of the foregoing, as a result, it has been found that: contain acrylic resin and silicon
In the adhesive composition of alkane coupling agent, by being applied in combination containing the more structural unit from polar functionalities monomer
The silane coupling agent of acrylic resin and the few oligomeric of alkoxy group content, it is excellent after embodying for a long time so as to obtain
Different re-workability and the adhesive that the albinism under the conditions of high temperature and humidity will not be caused.
That is, the 1st purport of the invention is, a kind of acrylic pressure-sensitive adhesive compositions contain: acrylic resin
(A)；With in the structure respectively containing 1 or more reactive functional groups and the silane coupling agent (B) of alkoxy, acrylic compounds
Resin (A) is comprising being originated from least one kind of polar functionalities monomer in hydroxyl monomer, carboxyl group-containing monomer, nitrogen containing monomer
(a1) acrylic resin of 5~50 weight % of structural unit, above-mentioned silane coupling agent (B) are 15 weights containing alkoxy group content
Measure % oligomeric silane coupling agent (B1) below.
And then the 2nd purport of the invention is that a kind of adhesive is the acrylic adhesives group of above-mentioned 1st purport
Made of conjunction object is crosslinked by crosslinking agent (C), the 3rd purport is, a kind of polarizer adhesive is using the 2nd purport
Made of adhesive, and then the 4th purport is, a kind of image display device, be with the adhesive of the 2nd purport by polarizer with
Made of liquid crystal cells are pasted.
The effect of invention
The present invention is a kind of acrylic pressure-sensitive adhesive compositions, is contained: acrylic resin (A) and being distinguished in the structure
Silane coupling agent (B) containing 1 or more reactive functional groups and alkoxy, above-mentioned acrylic resin (A) are to include source
Free self-contained carboxylic monomer, carboxyl group-containing monomer, at least one kind of polar functionalities monomer (a1) in nitrogen containing monomer structural unit 5
The acrylic resin of~50 weight %, above-mentioned silane coupling agent (B) are that 15 weight % are below oligomeric containing alkoxy group content
Object type silane coupling agent (B1).Therefore, the adhesive obtained using acrylic pressure-sensitive adhesive compositions of the invention is in manufacture figure
When as display device, as adhesive used in stickup of the polarizer (protective film) with liquid crystal cells (glass) in use, being
After the adhesive for embodying excellent re-workability and wet-heat resisting albefaction, excellent in te pins of durability for a long time, used as polarizer viscous
Mixture is highly useful.
When the reactive functional groups equivalent of above-mentioned oligomeric silane coupling agent (B1) is 1600g/mol or less, durability
It is more excellent.
When the weight average molecular weight of above-mentioned oligomeric silane coupling agent (B1) is 3000 or more, re-workability and durability are more
It is excellent.
When above-mentioned polar functionalities monomer (a1) at least contains carboxylic monomer, wet-heat resisting albefaction is more excellent.
Detailed description of the invention
Fig. 1 shows silane coupling agent " X-24-9589 "1HNMR spectrum.
Specific embodiment
Hereinafter, the present invention is described in detail.
It should be noted that respectively (methyl) acrylic acid refers to, acrylic or methacrylic acid, (first in the present invention
Base) acryloyl group refers to that acryloyl group or methylacryloyl, (methyl) acrylate refer to, acrylate or metering system
Acid esters.In addition, acrylic resin refers to, will the polymeric composition polymerization comprising at least one kind of (methyl) acrylate monomer and
Obtained resin.
Acrylic pressure-sensitive adhesive compositions of the invention contain acrylic resin (A) and silane coupling agent (B) conduct must
It must ingredient.
< acrylic resin (A) >
Acrylic resin (A) used in the present invention, it is necessary to for containing be originated from selected from hydroxyl monomer, contain carboxyl
The acrylic compounds tree of 5~50 weight % of structural unit of at least one kind of polar functionalities monomer (a1) in monomer, nitrogen containing monomer
Rouge, for example, it is preferable at least one kind of polar functionalities list in hydroxyl monomer, carboxyl group-containing monomer, nitrogen containing monomer will be included
Acrylic resin obtained from the copolymer composition copolymerization of 5~50 weight % of body (a1).
It in the copolymer composition of acrylic resin (A), may include as needed: (methyl) alkyl acrylate system monomer
(a2), other ethylenically unsaturated monomers that can be copolymerized (a3).
Firstly, at least one kind of polar functionalities monomer in hydroxyl monomer, carboxyl group-containing monomer, nitrogen containing monomer
(a1) it is illustrated.
As above-mentioned hydroxyl monomer, for example, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 4-
Hydroxybutyl, (methyl) acrylic acid 5- hydroxyl pentyl ester, the own ester of (methyl) acrylic acid 6- hydroxyl, (methyl) acrylic acid 8- hydroxyl monooctyl ester
The caprolactone modifications monomers, diethylene glycol such as equal hydroxyalkyl acrylates, caprolactone modification (methyl) acrylic acid 2- hydroxy methacrylate
Oxyalkylenes modified monomer and the phthalic acid 2- acryloyls such as (methyl) acrylate, polyethylene glycol (methyl) acrylate
Oxygroup ethyl -2- hydroxy methacrylate, N- methylol (methyl) acrylamide, hydroxyethyl acrylamide etc. contain primary hydroxy monomers；(first
Base) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 2- hydroxybutyl, (methyl) acrylic acid 3- chlorine 2- hydroxy propyl ester etc. contain secondary hydroxyl
Base monomer；The carboxylic monomers such as 2,2- dimethyl 2- hydroxyethyl (methyl) acrylate.
In above-mentioned hydroxyl monomer, from the reactivity of crosslinking agent in terms of excellent, in terms of wet-heat resisting albefaction improves
It sets out, preferably contains primary hydroxy monomers, stability aspect when polymerization, preferably (methyl) acrylic acid 2- hydroxy methacrylate,
From the aspect that the reactive fast, curing with crosslinking agent shortens, it is preferable to use (methyl) acrylic acid 4- hydroxybutyl.Further
, manufacture easy aspect, preferably (methyl) acrylic acid 2- hydroxy methacrylate, (first few from impurity such as two (methyl) acrylate
Base) acrylic acid 4- hydroxybutyl.
It should be noted that as above-mentioned hydroxyl monomer, further preferably used as two (methyl) acrylate of impurity
Containing ratio be 0.5 weight % or less person, particularly preferred 0.2 weight % or less, further preferred 0.1 weight % or less.Tool
For body, particularly preferred acrylic acid 2- hydroxy methacrylate, acrylic acid 4- hydroxybutyl, acrylic acid 2- hydroxy propyl ester.
As above-mentioned carboxyl group-containing monomer, for example, the acrylic acid such as (methyl) acrylic acid, P-carboxy ethyl acrylates
Dimeric dibasic acid etc., wherein the stability aspect in terms of wet-heat resisting albefaction, when polymerization, preferably (methyl) propylene
Acid.
As above-mentioned nitrogen atom monomer, for example, emulsion stability, amide-containing monomer etc..
As above-mentioned emulsion stability, for example, (methyl) acrylic-amino methyl esters, (methyl) acrylic-amino
The monomers containing secondary amino group such as the monomers containing primary amino group such as ethyl ester, (methyl) tbutylaminoethylacrylate, (methyl) acrylic acid ethyl
The tertiary-amino-containings monomers such as amino ethyl ester, (methyl) acrylate, (methyl) acrylic acid diethylamino ethyl ester
Deng.
In above-mentioned emulsion stability, from crosslinking facilitation effect it is high in terms of, the high aspect of the storage stability of resin,
It is preferred that tertiary-amino-containing monomer.
Moreover, the excellent adhesion aspect in terms of excellent in te pins of durability, with metal, metal oxide, preferably
The hetero ring types amine monomers such as (methyl) acryloyl morpholine.Wherein, particularly preferred (methyl) acrylate and (first
Base) acryloyl morpholine.
As amide-containing monomer, for example, (methyl) acrylamide；Methoxy (methyl) acrylamide,
Ethoxyl methyl (methyl) acrylamide, propoxy methyl (methyl) acrylamide, i-propoxymethyl (methyl) acrylamide,
Alkoxyalkyls (methyl) acryloyls such as n-butoxy methyl (methyl) acrylamide, isobutoxymethyl (methyl) acrylamide
Amine system monomer；Dialkyl group (methyl) the acrylamide lists such as dimethyl (methyl) acrylamide, diethyl (methyl) acrylamide
Body；The hydroxyls amide monomers such as N- (hydroxymethyl) acrylamide；(methyl) acryloyl morpholine；Deng.
In above-mentioned amide-containing monomer, in terms of the stability of resin solution, inhibit antistatic agent migration in terms of
It sets out, preferably alkoxyalkyl (methyl) acrylamide monomer, dialkyl group (methyl) acrylamide monomer.
In above-mentioned polar functionalities monomer (a1), from the excellent aspect of wet-heat resisting albefaction, it is preferable to use hydroxyl
Monomer.
In addition, above-mentioned polar functionalities monomer (a1), which can be used alone, can also be applied in combination two or more.From there is curing
It sets out in terms of the tendency to shorten, hydroxyl monomer and carboxyl group-containing monomer, hydroxyl monomer and tertiary amine system is further preferably applied in combination
Monomer.
Content as above-mentioned polar functionalities monomer (a1) (is applied in combination in situation of more than two kinds, contains for its total
Amount), relative to copolymer composition entirety, it is necessary to be 5~50 weight %, preferably 6~30 weight %, particularly preferred 7~25 weight %,
Further preferred 8~20 weight %.
If above-mentioned content is very few, has the tendency that wet-heat resisting albefaction reduction, if excessively, had as acrylic compounds
The tendency that the storage stability of resin solution reduces.
As polar functionalities monomer (a1), content when containing hydroxyl monomer is whole relative to copolymer composition, and preferably 5
~50 weight %, particularly preferred 6~35 weight %, further preferred 7~25 weight %, particularly preferred 8~20 weight %.
If the content of hydroxyl monomer is very few, has the tendency that wet-heat resisting albefaction reduction, if excessively, there is conduct
The tendency that the storage stability of acrylic resin solution reduces.
In addition, corrosion becomes the use of problem on the way, content phase when polar functionalities monomer (a1) is containing carboxyl group-containing monomer
For copolymer composition entirety, preferably 1 weight % or less.
As above-mentioned (methyl) alkyl acrylate system monomer (a2), for example, the carbon number of alkyl be usually 1~
20 (preferably 1~18, particularly preferred 1~12, further preferred 1~8) person, specifically, (methyl) acrylic acid first can be enumerated
Ester, (methyl) ethyl acrylate, (methyl) n-butyl acrylate, (methyl) isobutyl acrylate, (methyl) tert-butyl acrylate,
(methyl) n-propyl, (methyl) the just own ester of acrylic acid, (methyl) 2-EHA, (methyl) acrylic acid are just pungent
Ester, (methyl) isodecyl acrylate, (methyl) lauryl acrylate, (methyl) acrylic acid hexadecane ester, (methyl) acrylic acid are hard
Rouge ester etc..They, which can be used alone, can also be applied in combination two or more.
Wherein, from versatility, bonding physical properties excellent aspect, preferably methyl acrylate, ethyl acrylate, acrylic acid
N-butyl, 2-EHA.
The content of above-mentioned (methyl) alkyl acrylate system monomer (a2) is relative to copolymer composition entirety, preferably 20~95 weights
Measure %, particularly preferred 40~94 weight %, further preferred 45~93 weight %, in particular 50~92 weight %.
As the above-mentioned ethylenically unsaturated monomer that other can be copolymerized (a3), for example, (methyl) benzyl acrylate,
(methyl) phenoxyethyl acrylate, phenoxy group diethylene glycol (methyl) acrylate, (methyl) acrylic acid 2- hydroxyl -3- benzene oxygen
The monomers containing aromatic rings such as base propyl ester, (methyl) acrylic acid neighbour's phenylphenoxy ethyl ester；(methyl) cyclohexyl acrylate, (methyl) third
Olefin(e) acid cyclohexyl oxygroup alkyl ester, (methyl) t-butylcyclohexyl base oxygroup ethyl ester, (methyl) isobornyl acrylate, (first
Base) dicyclopentanyl acrylate etc. contains alicyclic monomers；(methyl) acrylic acid 2- methoxy acrylate, (methyl) acrylic acid 2- ethyoxyl second
Ester, (methyl) acrylic acid 3- methoxybutyl, (methyl) acrylic acid 2- butoxyethyl, 2- butoxy diethylene glycol (methyl) third
Olefin(e) acid ester, methoxyl group diethylene glycol (methyl) acrylate, methoxy triethylene (methyl) acrylate, ethyoxyl diethyl two
It is alcohol (methyl) acrylate, methoxyl group dipropylene glycol (methyl) acrylate, methoxy poly (ethylene glycol) (methyl) acrylate, pungent
It is oxygroup polyethylene glycol propylene glycol-mono- (methyl) acrylate, laurel acyloxy polyethyleneglycol (methyl) acrylate, hard
Ether-containings chain monomers such as acyl oxygroup polyethyleneglycol (methyl) acrylate etc..They, which can be used alone, to be applied in combination
Two or more.
Wherein, from be easily adjusted refractive index and it is birefringent in terms of, the excellent aspect of resistance to light leakage, preferably containing fragrance
Ring monomer (particularly preferred (methyl) benzyl acrylate, (methyl) phenoxyethyl acrylate, phenoxy group diethylene glycol (methyl) third
Olefin(e) acid ester), from being easily adjusted refractive index and side excellent in adhesion birefringent, to low polarity adherend (such as cycloolefin etc.)
Face is set out, and alicyclic monomers are preferably contained.
Using acrylic pressure-sensitive adhesive compositions of the invention as polarizer purposes in use, in terms of resistance to light leakage,
Preferably, the content of monomer containing aromatic rings, ester ring type monomer is adjusted, with birefringent the becoming smaller of the component entirety after endurance test
Mode, adjust the birefringent of adhesive.
As the content of the above-mentioned ethylenically unsaturated monomer that other can be copolymerized (a3), preferably 35 weight % or less, further
It is preferred that 25 weight % or less.Other ethylenically unsaturated monomers that can be copolymerized (a3) have inclining for resistance to light leakage reduction if excessive
To.
Acrylic resin used in the present invention (A) is suitable for selecting polar functionalities monomer (a1), preferably further fitting
(methyl) alkyl acrylate system monomer (a2), other ethylenically unsaturated monomers that can be copolymerized (a3) are preferably selected, it is poly- using these
Synthesis point, such as in organic solvent, mix or be added dropwise above-mentioned polymeric composition, polymerization initiator and polymerize, so as to manufacture.
Above-mentioned polymerization reaction can be previous public by solution free radical polymerization, suspension polymerisation, bulk polymerization, emulsion polymerization etc.
The polymerization known and carry out, wherein preferred solution free radical polymerization, bulk polymerization, particularly preferred solution free radical polymerization.
As organic solvent used in above-mentioned polymerization reaction, for example, toluene, dimethylbenzene etc. it is aromatic hydrocarbon,
The aliphatic such as the esters such as the aliphatic hydrocarbons such as hexane, ethyl acetate, butyl acetate, normal propyl alcohol, isopropanol alcohols, acetone, first and second
Ketones such as ketone, methyl iso-butyl ketone (MIBK), cyclohexanone etc..
It is dry when being coated from the easiness, the effect of chain tra nsfer, adhesive of polymerization reaction to be easy in these organic solvents
Property, highly-safe aspect is set out, it is preferable to use ethyl acetate, acetone, methyl ethyl ketone, butyl acetate, toluene, methyl-isobutyl
Ketone, further preferred ethyl acetate, acetone, methyl ethyl ketone.
These organic solvents, which can be used alone, can also be applied in combination two or more.
In addition, as polymerization initiator used in above-mentioned solution free radical polymerization, for example, common freedom
Base polymerization initiator, i.e., the double -2- methylbutyronitrile of 2,2 '-azobis isobutyronitriles, 2,2 '-azos, bis- (the 4- cyano penta of 4,4 '-azos
Acid), azo initiators, benzoyl peroxide, lauroyl peroxide, the di-t-butyl mistake such as 2,2 '-azos bis- (methylpropanoic acids)
Organic peroxides such as oxide, cumene hydroperoxide etc. can be suitable for selecting and using according to the monomer used.These are poly-
Conjunction initiator, which can be used alone, can also be applied in combination two or more.
Acrylic resin used in the present invention (A) must contain the structural unit from polar functionalities monomer (a1)
5~50 weight %, preferably 6~35 weight %, particularly preferred 7~25 weight %, further preferred 8~20 weight %.From containing
If the structural unit of polar group monomer is very few, wet-heat resisting albefaction becomes to reduce, if excessively, to form acrylic acid
The tendency that storage stability when resinoid solution reduces.
The weight average molecular weight preferably 600,000~2,500,000 of above-mentioned acrylic resin (A), it is particularly preferred 800,000~2,000,000, into
One step preferably 1,000,000~1,800,000, particularly preferred 1,100,000~1,600,000.
If above-mentioned weight average molecular weight is too small, have the tendency that durability reduction, is needed if excessive, when manufacturing a large amount of
Retarder thinner has drying property reduction, and residual solvent becomes more within the adhesive layer, the tendency that heat resistance reduces.
The dispersion degree (weight-average molecular weight/number-average molecular weight) preferably 10 or less of above-mentioned acrylic resin (A), particularly preferably
7 or less, further preferred 5 or less.
If above-mentioned dispersion degree is excessively high, have the tendency that re-workability reduces or durability reduces.It should be noted that
The lower limit of above-mentioned dispersion degree is usually 1.
It should be noted that above-mentioned weight average molecular weight is the weight average molecular weight to be converted based on standard polystyren molecular weight,
High performance liquid chromatograph (Japanese Waters corporation, " Waters 2695 (main body) " and " Waters 2414 (detector) ") makes
With column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 107, separating ranges: 100~2 × 107, theoretical cam curve:
10000 grades/root, filler material: styrene diethylene benzene copoly mer, filler partial size: 10 μm) 3 series connection, thus
Measurement, number-average molecular weight can also be measured with same method.Moreover, dispersion degree is asked by weight average molecular weight and number-average molecular weight
Out.
Preferably -60~0 DEG C of the glass transition temperature (Tg) of above-mentioned acrylic resin (A), particularly preferably -50~-20
DEG C, further preferably -45~-25 DEG C.
If above-mentioned glass transition temperature is excessively high, have the tendency that adhesion becomes easy reduction, if too low, has resistance to
Hot reduced tendency.
It should be noted that above-mentioned glass transition temperature is calculated by the formula of following Fox.
Tg: the glass transition temperature (K) of acrylic resin (A)
Tga: glass transition temperature (K) Wa: the weight fraction of monomer A of the homopolymer of monomer A
Tgb: glass transition temperature (K) Wb: the weight fraction of monomer B of the homopolymer of monomer B
Tgn: the weight fraction (Wa+Wb++ of glass transition temperature (K) Wn: monomer N of the homopolymer of monomer N
Wn=1)
That is, the glass transition temperature (Tg) of acrylic resin (A) refers to, each of acrylic resin (A) will be constituted
Glass transition temperature and weight fraction when monomer forms homopolymer are substituting to the formula of Fox and the value that calculates.
It should be noted that the glass transition temperature when monomer for constituting acrylic resin (A) forms homopolymer leads to
Often using differential scanning calorimetry (DSC) (DSC) and measure, can use foundation JIS K7121-1987, JIS K 6240 method and
Measurement.
The refractive index of above-mentioned acrylic resin (A) is usually 1.440~1.600, preferably 1.460~1.550, it is especially excellent
Select 1.470~1.500.Above-mentioned refractive index is preferably, and reduces the refringence of the component of stacking, the light loss of component interface
Mistake becomes smaller.
Above-mentioned refractive index is following value: it uses refractive index measuring apparatus (Atago corporation " Abbe refractometer 1T "), with
NaD ray, 23 DEG C of measurements form the value of the acrylic resin (A) of film.
It is the mist degree preferably 1.0 or less of above-mentioned acrylic resin (A) single layer, particularly preferred 0.8 or less, further preferably
0.5 or less.If above-mentioned mist degree is excessively high, have the tendency that the image quality for the display for using it as adhesive reduces.
Mist degree calculates as follows: saturating using HAZE MATER NDH2000 (Nippon Denshoku Industries Co., Ltd.'s system) measurement diffusion
Rate and total light transmittance are penetrated, gained diffused transmission rate and the value of total light transmittance are substituted into following formula and is calculated.It should be noted that this
Machine is according to JIS K7361-1.
Mist degree (%)=(diffused transmission rate/total light transmittance) × 100
Acrylic resin (A) used in the so available present invention.
< silane coupling agent (B) >
It is organic containing 1 or more reactive functional groups and alkoxy respectively in the structure in general, silane coupling agent refers to
Silicon compound.
In the present invention, as the silane coupling agent in the structure respectively containing 1 or more reactive functional groups and alkoxy
It (B), is 15 weight % oligomeric silane coupling agent (B1) below containing alkoxy group content.
The alkoxy limited in the present invention refers to the alkoxy from alkoxy silane, does not include in molecule in addition to this
Contained alkoxy.
For example, the end in the polyethers portion of polyether modified silicane, polyether structure include not as alkoxy.
As above-mentioned reactive functional groups, for example, epoxy group, (methyl) acryloyl group, sulfydryl, hydroxyl, carboxylic
Base, amino, amide groups, isocyanate group etc..Wherein, the aspect excellent from durability, re-workability, preferably epoxy group,
Sulfydryl.
As above-mentioned alkoxy, for example, methoxyl group, ethyoxyl, propoxyl group etc..Wherein, preferred carbon number 1~8
The alkyl of alkyl, particularly preferred carbon number 1~2, specifically, being methoxyl group, ethyoxyl.
It should be noted that silane coupling agent (B) organic taking of can have in addition to reactive functional groups and alkoxy
Dai Ji, such as alkyl, phenyl.
The alkoxy group content of oligomeric silane coupling agent (B1) be necessary for 15 weight % hereinafter, it is preferred that 1~15 weight %,
Particularly preferred 3~14.5 weight %, further preferred 5~14.5 weight %.
If above-mentioned alkoxy group content is excessive, have the tendency that long-term re-workability reduces.It should be noted that if mistake
It is few, then have the tendency that durability reduction.
The weight average molecular weight preferably 3000 or more of oligomeric silane coupling agent (B1), it is particularly preferred 4000~30000, into
One step preferably 4500~20000.
If above-mentioned weight average molecular weight is in above range, there is the harmony of long-term re-workability and durability excellent
Tendency.
It should be noted that above-mentioned weight average molecular weight is the weight average molecular weight based on the conversion of standard polystyren molecular weight,
It can be measured by following methods.
Device: gel permeation chromatograph
Detector: differential refraction rate detector RI (TOSOH Co., Ltd's RI-8020 type, sensitivity 32)
Column: TSKgel guardcolumn HHR- H (1) (TOSOH Co., Ltd φ 6mm × 4cm), TSKgel
GMHHR- N (2) (TOSOH Co., Ltd φ 7.8mm × 30cm)
Solvent: tetrahydrofuran (THF)
Column temperature: 23 DEG C
Flow velocity: 1.0mL/ minutes
In addition, the preferred 1600g/mol or less of reactive functional groups equivalent of oligomeric silane coupling agent (B1), especially excellent
Select 100~900g/mol, further preferred 300~700g/mol.
Above-mentioned reactive functional groups equivalent has durability more excellent tendency if it is above range.
Oligomeric silane coupling agent (B1) is the silane coupling agent of oligomeric, is organo-silicon compound in other words
Organo-silicon compound (the organosiloxane compound of the oligomerics such as dimer, tripolymer made of a part hydrolysis and polycondensation
Object).
As oligomeric silane coupling agent (B1), for example, γ-epoxy propoxy propyl triethoxysilane,
Oligomer made of a part hydrolysis and polycondensation of the organo-silicon compound such as γ-glycidoxypropyl diethoxy silane
Type organo-silicon compound (organosilan oxygroup oligomer containing epoxy group etc.) or by these oligomeric organo-silicon compound
The silane coupling agents of the oligomerics containing epoxy group such as oligomeric organo-silicon compound made of a part is modified through ether；γ-mercapto
Oligomeric organo-silicon compound made of a part hydrolysis and polycondensation of the organo-silicon compound such as base propyl-triethoxysilicane
Silane coupling agent of the oligomerics containing sulfydryl such as (organosilan oxygroup oligomer containing sulfydryl etc.)；Deng.
Wherein it is possible to be suitable for selecting and using in a manner of each condition for meeting oligomeric silane coupling agent (B1).Separately
Outside, above-mentioned oligomeric silane coupling agent (B1) can be used only a kind, two or more can also be applied in combination.
As oligomeric silane coupling agent (B1), specifically, Shin-Etsu Chemial Co., Ltd can be enumerated
Commercially available product, that is, " X-24-9590 " (weight average molecular weight: 13700, contains alkoxy: methoxyl group, alkoxy group content: 9.5 weights
Amount %, reactive functional groups: epoxy group, epoxide equivalent: 592g/mol), " X-24-9589 " (weight average molecular weight: 4700, contain
Alkoxy: ethyoxyl, alkoxy group content: 13.2%, reactive functional groups: epoxy group, epoxide equivalent: 1509g/mol) etc..
Wherein, particularly preferably " X-24-9590 ".
The content of oligomeric silane coupling agent (B1) is relative to 100 parts by weight of acrylic resin (A), and preferably 0.001
~1 parts by weight, particularly preferred 0.015~0.5 parts by weight, further preferred 0.020~0.3 parts by weight, further preferred 0.025
~0.15.If above-mentioned content is excessive, have the tendency that durability reduction, if very few, there is long-term re-workability to reduce
Tendency.
It should be noted that in acrylic pressure-sensitive adhesive compositions of the invention, in the range for not interfering The effect of invention
It is interior, the silane coupling agent in addition to above-mentioned oligomeric silane coupling agent (B1), the content of the silane coupling agent can be used
If excessive, have the tendency that due to exudation and durability reduction.Therefore, in addition to above-mentioned oligomeric silane coupling agent (B1)
Silane coupling agent content specifically, relative to 100 parts by weight of acrylic resin (A), below preferably 0.5 parts by weight,
Below further preferred 0.3 parts by weight, below particularly preferred 0.1 parts by weight.
In acrylic pressure-sensitive adhesive compositions of the invention, except above-mentioned acrylic resin (A) and silane coupling agent (B) with
Outside, crosslinking agent (C), antistatic agent (D) are preferably comprised.
< crosslinking agent (C) >
As crosslinking agent (C), for example, isocyanates system crosslinking agent, epoxy crosslinking agent, the crosslinking of aziridine system
Agent, melamine series crosslinking agent, aldehyde system crosslinking agent, amine system crosslinking agent, metallo-chelate system crosslinking agent, wherein from raising and base
The aspect of the cementability of material, the aspect excellent with the reactivity of acrylic resin (A) are set out, it is preferable to use isocyanates system hands over
Join agent.
As above-mentioned isocyanates system crosslinking agent, for example, 2,4- toluene di-isocyanate(TDI)s, 2,6- toluene two are different
The xylylene diisocyanates systems such as the toluene di-isocyanate(TDI)s such as cyanate system crosslinking agent, 1,3- xylylene diisocyanate hand over
Join two isocyanides of naphthalenes such as diphenylmethanes crosslinking agent, the 1,5- naphthalene diisocyanates such as agent, diphenyl methane -4,4- diisocyanate
The aromatic systems isocyanates such as acid esters system crosslinking agent system crosslinking agent；Isophorone diisocyanate, 1,4- hexamethylene diisocyanate
Ester, 4,4 '-dicyclohexyl methyl hydride diisocyanates, methylcyclohexane diisocyanate, isopropylidene dicyclohexyl -4,4 '-two
Isocyanates, 1,3- diisocyanate root close the alicyclic ring families isocyanates systems such as hexahydrotoluene, norbornene alkyl diisocyanate and hand over
Join agent；The fatty families isocyanates such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate system crosslinking agent；With
Adduct, biuret, isocyanuric acid ester body of above-mentioned isocyanates based compound etc..
In these isocyanates system crosslinking agents, from working life and durability aspect, preferably toluene di-isocyanate(TDI)
Be crosslinking agent, from shorten curing time aspect, preferably xylylene diisocyanate system crosslinking agent or contain isocyanuric acid
The isocyanates system crosslinking agent of ester skeleton, from yellowing resistance aspect, preferably non-aromatic is non-hands over containing isocyanates system
Join agent.Wherein, specifically, the aspect excellent from the harmony of durability, working life, crosslinking rate, preferably toluene two
Isocyanates, xylylene diisocyanate, hexamethylene diisocyanate and trimethylolpropane adduct and isocyanide urea
Acid esters body.
As above-mentioned epoxy crosslinking agent, for example, the epoxy resin of bisphenol A/epichlorohydrin type, ethylene glycol
Diglycidyl ether, polyethyleneglycol diglycidylether, glycerin diglycidyl ether, T 55,1,6- oneself two
Alcohol diglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, d-sorbite polyglycidyl ether, polyglycereol poly epihydric alcohol
Ether, pentaerythrite poly epihydric alcohol antierythrite, two glycerine polyglycidyl ethers etc..
As above-mentioned aziridine system crosslinking agent, for example ,-three-β of tetramethylol methane-'-aziridino propionic ester,
- three-β of trimethylolpropane-'-aziridino propionic ester, N, N '-diphenyl methane -4,4 '-bis- (1- aziridine Carboxylamide), N,
N '-hexa-methylene -1,6- bis- (1- aziridine Carboxylamides) etc..
As above-mentioned melamine series crosslinking agent, for example, hexamethoxymethyl melamine, six (ethoxymethyl)s
Base melamine, six propoxy methyl melamines, six butoxymethyl melamines, six amyl oxygroup methyl melamines,
Six hexyl oxygroup methyl melamines, melamine resin etc..
As above-mentioned aldehyde system crosslinking agent, for example, glyoxal, malonaldehyde, succinaldehyde, malealdehyde, penta 2
Aldehyde, formaldehyde, acetaldehyde, benzaldehyde etc..
As above-mentioned amine system crosslinking agent, for example, hexamethylene diamine, triethyl group diamines, polyethyleneimine, six
Methenamine, diethylenetriamines, trientine, isophorone diamine, amino resins, polyamide etc..
As above-mentioned metallo-chelate system crosslinking agent, for example, aluminium, iron, copper, zinc, tin, titanium, nickel, antimony, magnesium, vanadium,
Acetylacetone,2,4-pentanedione, acetylacetic ester complex of the polyvalent metals such as chromium, zirconium etc..
Above-mentioned crosslinking agent (C) may be used singly or in combination of two or more.
The content of above-mentioned crosslinking agent (C) relative to 100 parts by weight of acrylic resin (A), preferably 0.01~5 parts by weight,
Particularly preferred 0.05~1.5 parts by weight, further preferred 0.1~0.5 parts by weight.
If above-mentioned content is very few, have the tendency that durability is easily reduced, if excessively, there is stress retentivity drop
The tendency that low, substrate becomes easy warpage or needs to cure for a long time.
< antistatic agent (D) >
In acrylic pressure-sensitive adhesive compositions of the invention, preferably further contain antistatic agent (D), as antistatic agent
(D), it is particularly suitable that, ionic compound (D1).
As above-mentioned ionic compound (D1), from static countermeasure aspect, preferably comprise by metal salt and organic
The ionic compound that at least one of salt is formed.
As metal salt, for example, the alkali metal salts such as lithium salts, sodium salt, calcium salt, sylvite or alkali salt, Phosphonium
Salt.
As organic salt, for example, ammonium salt, imidazole salts, pyridiniujm, piperidinium salt, Pyrrolizidine salt, sulfonium
The salt such as salt.
Wherein, from anticorrosion it is excellent in terms of, long-term re-workability it is excellent in terms of, excellent storage stability in terms of go out
Hair, preferably organic salt, more preferably by ammonium cation, glyoxaline cation, pyridylium, piperidines cation, Pyrrolizidine
The salt that the cationic nitrogenous such as cation are formed, can particularly preferably enumerate alkylammonium salt, four alkane of further preferred non-annularity
Base ammonium cation and N, ammonium salt, ammonium cation and the N that bis- (trifluoro methylsulfonyl) the imines anion of N- are formed, N- bis- (fluorosulfonyls)
The ammonium salt etc. that imide anion is formed.
Preferably 10 DEG C~100 DEG C of the fusing point of ionic compound (D1), it is 20 DEG C~80 DEG C particularly preferred, further preferred 25
~50 DEG C.If above-mentioned fusing point is excessively high, has the tendency that being easy precipitation at low temperature, if too low, have under hygrothermal environment
It is easy to produce the tendency of the decoloration of polarizer.
The content of antistatic agent (D) is relative to 100 parts by weight of acrylic resin (A), preferably 0.5~10 parts by weight, more
It is preferred that 2~8 parts by weight, further preferred 2~5 parts by weight, particularly preferred 2.5~4.5 parts by weight.If above-mentioned content is very few,
It is then unable to get antistatic property, the tendency that display is uneven caused by electrostatic is easy to produce, if excessively, there is polarizer
Degree of polarization reduce or wet-heat resisting albefaction reduce or exudation and durability reduce tendency.
It in turn,, can be in the range of not impairing the effect of the present invention in acrylic pressure-sensitive adhesive compositions of the invention
Compounded resin ingredient, acrylic monomers, polymerization inhibitor, antioxidant, anticorrosive, crosslinking accelerator, free-radical generating agent, peroxide
The various additives such as compound, free radical scavenger, metal and resin particle etc. are used as other compositions.In addition, apart from the above, it can
With impurity contained in manufacture raw material of constituent containing a small amount of adhesive composition etc. etc..
The content of above-mentioned other compositions is relative to 100 parts by weight of acrylic resin (A), below preferably 5 parts by weight, especially
It is preferred that below 1 parts by weight, below further preferred 0.5 weight.If above-mentioned content is excessive, have and acrylic resin (A)
Compatibility reduce, wet-heat resisting albefaction reduce tendency.
So by by acrylic resin (A) and silane coupling agent (B), crosslinking agent as needed (C), antistatic agent
(D) it is mixed with other compositions, so as to obtain acrylic pressure-sensitive adhesive compositions of the invention.It should be noted that for
Mixed method is not particularly limited, and can use: by each ingredient while mixed method；It, will be remaining after any ingredient is mixed
The various methods such as the method that simultaneously or sequentially mixes of ingredient.
Acrylic pressure-sensitive adhesive compositions of the invention are by being solidified and (being crosslinked), so as to form adhesive, into
And by the way that the adhesive phase for being formed and being formed by above-mentioned adhesive is laminated on optical component (optical laminate), so as to
To the optical component with adhesive phase.
It is preferably enterprising in the face opposite with optical component face of adhesive phase for the above-mentioned optical component with adhesive phase
Release sheet is arranged in one step.
As the manufacturing method of the above-mentioned optical component with adhesive phase, can enumerate:
Method (1) is bonded release sheet, in room after being coated with acrylic pressure-sensitive adhesive compositions on optical component and drying
The processing using curing is carried out under warm at least one of (23 DEG C) or warm-up mode；
(method 2) is bonded optical component, in room after being coated with acrylic pressure-sensitive adhesive compositions on release sheet and drying
The processing using curing is carried out under at least one of temperature or warm-up mode；
Deng.Wherein, the aspect in terms of not damaging optical component, excellent in adhesion with optical component is set out, preferably (2)
Method in, the method that is cured under room temperature state.
It in the case where being polarizer is particularly effective as optical component it should be noted that among the above.
For above-mentioned maturation process, the reaction time of the chemical crosslinking as adhesive, to bond physical property to obtain
Harmonious and time for carrying out, as the condition of curing, it is usually 1~30 day that temperature, which is usually room temperature~70 DEG C, time, specifically
For, such as can be carried out at 23 DEG C with 1~20 day, at 23 DEG C with 3~10 days, at 40 DEG C with the conditions such as 1~7 day.
When the coating of above-mentioned adhesive composition, the acrylic pressure-sensitive adhesive compositions are diluted in a solvent preferably and are applied
Cloth, as diluted concentration, in terms of solid component concentration, preferably 5~60 weight %, particularly preferred 10~30 weight %.
In addition, being not particularly limited as long as dissolving acrylic pressure-sensitive adhesive compositions, such as can as above-mentioned solvent
To use the ester series solvents such as methyl acetate, ethyl acetate, methyl acetoacetate, ethyl acetoacetate, acetone, methyl ethyl ketone, methyl
The alcohol series solvents such as the aromatic systems such as the ketone series solvents such as isobutyl ketone, toluene, dimethylbenzene solvent, methanol, ethyl alcohol, propyl alcohol.Wherein, from
Dissolubility, drying property, price etc. are set out, and are suitble to use ethyl acetate, methyl ethyl ketone.
In addition, the coating about above-mentioned acrylic pressure-sensitive adhesive compositions, is applied by roller coating, die coating, intaglio plate coating, comma
The common method such as cloth, silk-screen printing and carry out.
Gel fraction for the adhesive phase manufactured by the above method from endurance quality and inhibits degree of polarization to reduce
Aspect is set out, preferably 30~95 weight %, particularly preferred 40~90 weight %, further preferred 60~85 weight %.Gel point
If rate is too low, have the tendency that re-workability reduction, if excessively high, has the tendency that becoming easy generation floats, removes.
Above-mentioned gel fraction becomes the index of the degree of cross linking (curing degree degree), thus, for example being calculated with following methods.That is,
Bonding sheet made of adhesive phase is formed using the acquisition bonding of picking device from optical component, especially from substrates such as polarizers
Adhesive is coated on the SUS metal mesh of 200 mesh by agent, is impregnated in the ethyl acetate for be adjusted to 23 DEG C 24 hours, will be remained
The weight percent of undissolved adhesive ingredients in metal mesh is as gel fraction.
It should be noted that when the gel fraction of adhesive is adjusted to above range, it can be by adjusting crosslinking agent
Type and amount etc. and reach.
There is more good adhesion sense person for practical patch for the adhesive phase manufactured by the above method, when touching with finger
Wettability in adherend is good, therefore, has the tendency that workability raising, is preferred.
As the electrical characteristics for the adhesive phase for using acrylic resin composition of the invention to obtain, sheet resistance value is excellent
Select 1 × 1012Ω or less, particularly preferred 1 × 1011Ω or less, further preferred 5 × 1010Ω or less.Above-mentioned sheet resistance value is such as
Fruit is excessively high, then polarizer, adhesive phase are easy electrification, has the tendency that becoming easy and causes display uneven.
In addition, preferably 5~200 μm of the thickness of the adhesive phase after drying in optical component of the gained with adhesive phase,
Particularly preferred 10~100 μm, it is 10~30 μm further preferred.If above-mentioned thickness is excessively thin, there is bonding physical property to be not easy stable
Tendency has from the moisture of end if blocked up and immerses the tendency that quantitative change is more, and long-term re-workability reduces.
It, directly will bonding for the optical component with adhesive phase, especially with the polarizer of adhesive phase in the present invention
Adhesive phase face is fitted in glass substrate after on the glass substrate or when having release sheet removing release sheet by the conjunction of oxidant layer face paste
On, it is supplied to such as image display device.
The bonding force (re-workability) of adhesive of the invention is suitable for determining according to material of adherend etc..
For example, when being fitted in the glass substrates such as liquid crystal cells, in terms of the bonding force after being bonded 1 day, preferably 0.1~10N/
25mm, further preferred 0.1~5N/25mm.In addition, in terms of the bonding force after 20 days, preferably 0.1~20N/25mm, further
It is preferred that 0.1~15N/25mm, particularly preferred 0.1~10N/25mm.In turn, in terms of the bonding force after 50 days, preferably 0.1~20N/
25mm, further preferred 0.1~15N/25mm, particularly preferred 0.1~10N/25mm.
Above-mentioned bonding force calculates as follows.
For the polarizer with adhesive phase, wide 25mm is cut into, mould release film is removed, adhesive phase side is pressed into
Alkali-free glass plate (Corning Incorporated's system, " EAGLE XG "), is bonded polarizer with glass plate.Later, autoclave process (50 is carried out
DEG C × 0.5MPa × 20 minute) after, after being placed 24 hours at 23 DEG C × 50%RH, in 180 ° of peel angle, peeling rate
Lower progress disbonded test in 300mm/ minutes.Moreover, about long-term re-workability, after autoclave process, in 23 DEG C × 50%RH
After time as defined in lower placement, in 180 ° of peel angle, under peeling rate 300mm/ minutes disbonded test is carried out.
The available durability of acrylic pressure-sensitive adhesive compositions of the invention and wet-heat resisting albefaction are excellent and save steady
Qualitative, re-workability also harmonious good and excellent adhesive, as optical component adhesive, particularly make polarizer with
The polarizer of the stickups such as glass substrate is useful with adhesive.
As the protective film for constituting polarizer, tri acetic acid fiber prime system film, acrylic film, polyethylene can be enumerated
It is film, polypropylene-based film, cyclic olefine film etc., the present invention can be suitble to make to using the polarizer of any protective film
With setting out in terms of being easy to get effect of the invention, be particularly preferably laminated with the polarizer of cycloolefin film.
In addition, by using above-mentioned adhesive, so as to so that polarizer and liquid crystal cells are pasted and make image and show
Device, gained image display device can precisely make, and durability becomes excellent.
Embodiment
The present invention is further specifically illustrated hereinafter, enumerating embodiment, but the present invention is as long as being no more than its purport
It is not limited to the following embodiments.It should be noted that " part ", " % " refer to weight basis in example.
Firstly, preparing various acrylic resins as following.It should be noted that about acrylic resin (A) and silicon
The weight average molecular weight of alkane coupling agent (B), dispersion degree, glass transition temperature are measured according to preceding method.
It should be noted that the measurement about viscosity, according to JIS K5400 (1990) 4.5.3 rotational viscometer method and
Measurement.
< acrylic resin (A) >
(manufacture of acrylic resin (A-1))
In the four round flask for having reflux condenser, blender, the mouth blown of nitrogen and thermometer, propylene is put into
Sour 6 parts of 2- hydroxy methacrylate (a1), 0.7 part of acrylic acid (a1), 73.3 parts of n-butyl acrylate (a2), benzyl acrylate (a3) 20
Part, 53 parts of ethyl acetate, 42 parts of acetone, 0.013 part of the azobis isobutyronitrile (AIBN) as polymerization initiator rise interior temperature
To boiling point, start reaction.Then, 30 parts of ethyl acetate solution comprising AIBN 0.04% are added dropwise, react at a reflux temperature
It after 3.25 hours, is diluted with ethyl acetate, obtains acrylic resin (A-1) solution (solid component 20.9%, viscosity
4770mPas/25 DEG C, acrylic resin (A-1): -43 DEG C of glass transition temperature, weight average molecular weight 1,290,000, dispersion degree
4.3)。
Monomer used in above-mentioned uses the product of following manufacturers.
Acrylic acid 2- hydroxy methacrylate (Tg-15 DEG C of Osaka organic chemistry Co. Ltd. system)
Acrylic acid (Tg106 DEG C of Mitsubishi chemical Co., Ltd)
Butyl acrylate (Tg-56 DEG C of Mitsubishi chemical Co., Ltd)
Benzyl acrylate (Viscoat#160Tg6 DEG C of Osaka organic chemistry Co. Ltd. system)
In addition, above-mentioned Tg is the Tg of the homopolymer of each monomer.
(acrylic resin (A-2)~(A-4) and (A ' -1), (A ' -2) manufacture)
Using copolymer composition recorded in table 1, the manufacturing method according to above-mentioned acrylic resin (A-1) is carried out, is obtained
Acrylic resin (A-2)~(A-4) and (A ' -1), (A ' -2) solution.In addition, gained acrylic resin (A-2)~(A-4)
It is recorded in (A ' -1), (A ' -2) solution such as table 1.
[table 1]
< silane coupling agent (B) >
As silane coupling agent (B), prepare substance below.It should be noted that the weight about silane coupling agent (B) is equal
Molecular weight is measured according to preceding method.In addition, working as alkoxy group content, reactive functional groups, epoxide equivalent or sulfydryl
It measures, contain alkoxy, just use Directory Value as long as no limiting.
(B1-1):
(Shin-Etsu Chemial Co., Ltd's system, " X-24-9590 ", weight average molecular weight: 13700, alkoxy group content:
9.5%, reactive functional groups: epoxy group, epoxide equivalent: 592g/mol, contain alkoxy: methoxyl group)
(B1-2):
(Shin-Etsu Chemial Co., Ltd's system, " X-24-9589 ", weight average molecular weight: 4700, alkoxy group content: 14.5%
(measured value), reactive functional groups: epoxy group, epoxide equivalent: 1509g/mol, contain alkoxy: ethyoxyl: ethyoxyl and third
Alkenyl oxygroup)
It should be noted that the alkoxy group content about " X-24-9589 ", measures by the following method, alcoxyl is carried out
The calculating of base content.
1. measurement
Sample about 50mg is weighed in the vial, and d- chloroform 1mL is added and makes it dissolve, prepares 5% (w/v) chloroformic solution.It will
It is put into NMR test sample test tube, carries out under the following conditions1HNMR measurement.By gained1HNMR spectrum is shown in Fig. 1.
" determination condition "
Measurement device: Bruker corporation AscendTM400
Probe: cryo probe
Pulse protocol: pulse
Measuring temperature: 23 DEG C (296K)
Cumulative frequency: 16 times
Pulse delay time: 10 seconds
2. the calculating of alkoxy group content
For1Signal A~F of HNMR spectrum is attributed to A (6.2,6.0ppm): acrylic oxygroup, B (3.6ppm): epoxy
Ethane chain, C (3.4ppm): ethylene oxide chain end methoxyl group, D (3.1,2.8,2.6ppm): epoxy group, E (1.2ppm): ethoxy
Base, F (0.1ppm): methyl finds out alkoxy group content according to the integrated value of these signals.
It should be noted that organic substituent (epoxy group, methyl) number is set as X, alkoxy (ethyoxyl, acrylic oxygen
Base) number is set as R, the main chain (- SiO-) containing (X+R)/2.
·(B’-1)
(Shin-Etsu Chemial Co., Ltd's system, " X-41-1059A ", weight average molecular weight: 2270, alkoxy group content: 42%,
Reactive functional groups: epoxy group, epoxide equivalent: 350g/mol, contain alkoxy: methoxyl group, ethyoxyl)
·(B’-2)
(Shin-Etsu Chemial Co., Ltd's system, " X-41-1805 ", weight average molecular weight: 3450, alkoxy group content: 50%,
Reactive functional groups: sulfydryl, mercapto equivalents: 800g/mol, contain alkoxy: methoxyl group, ethyoxyl)
·(B’-3)
(Shin-Etsu Chemial Co., Ltd's system, " X-41-1810 ", weight average molecular weight: 640, alkoxy group content: 30%, anti-
Answering property functional group: sulfydryl, mercapto equivalents: 450g/mol, contain alkoxy: methoxyl group)
·(B’-4)
3- glycidoxypropyltrime,hoxysilane (Shin-Etsu Chemial Co., Ltd's system, " KBM-403 ", molecular weight:
236.6, alkoxy group content: 39% (calculated value), reactive functional groups: epoxy group, epoxide equivalent: 236.6g/mol (is calculated
Value), contain alkoxy: methoxyl group)
It should be noted that about B ' -4 alkoxy group content, using the weight of methoxyl group divided by obtained from molecular weight
It is worth (the weight of 3, methoxyl groups of methoxy radix；31, molecular weight 236.6).Epoxide equivalent is with point relative to epoxy group 1mol
Son amount calculates.
< crosslinking agent (C) >
As crosslinking agent (C), prepare following substance.
(C-1): adduct (the TOSOH Co., Ltd's system, " CORONATE of toluene di-isocyanate(TDI) and trimethylolpropane
L55E”)
< antistatic agent (D) >
As antistatic agent (D), prepare following substance.
(D-1): three positive fourth methyl ammonium N, N- bis- (trifluoro methylsulfonyl) imines (3M corporation, " FC-4400 ", fusing points 27.5
℃)
(D-2): by ionic compound (the first industry system formed containing fragrant cyclic ammonium cation and bis- (fluorine sulfimides)
Medicine Co. Ltd. system, " MP-446 ", 37 DEG C of fusing point)
(D-3): bis- (trifluoro methylsulfonyl) imine lithiums of N, N- (gloomy field Chemical Co., Ltd. system, " Li-TFSI ", fusing point 232~
234℃)
< embodiment 1~12,1~9 > of comparative example
If following table 2 is compounded mentioned component (A)~(D), solid component concentration is adjusted to 12.5% with ethyl acetate, is obtained
To acrylic pressure-sensitive adhesive compositions.
[table 2]
Note) resin in () is compounding parts by weight in terms of solid component.
Using acrylic pressure-sensitive adhesive compositions obtained in above-mentioned, such as following production sample for evaluations, to following performances
It is evaluated.Show the results of the evaluation aftermentioned table 3.
(production of polarizer [I], [II] with adhesive phase)
Gained acrylic pressure-sensitive adhesive compositions are coated on to 38 μm of thickness of release sheet (Mitsui Chemicals TOHCELLO company
Make " Lumirror SP-0138BU ") so that the thickness after dry becomes 25 μm, after 3 minutes dry at 100 DEG C, make and take off
Matrix is that the adhesive level of opposite side is pasted onto one that two sides is laminated with the polarizer of cellulose triacetate (TAC) film
TAC film surface cures 7 days in the environment of 23 DEG C × 50%RH, and obtaining the polarizer [I] with adhesive phase, (layer is constituted；It is de-
Matrix/adhesive phase/1/ polarizing film of TAC film/TAC film 2, TAC film 1: 40 μm of thickness, 2:60 μm of TAC film).
Keep the cyclic olefine film/polarizing film/TAC system film face COP for implementing sided corona treatment and adhesive level viscous
Patch, in addition to this, gets similarly the polarizer [II] with adhesive phase.
It should be noted that above-mentioned TAC film is triacetate cellulose film (60 μm of thickness), COP film is cycloolefin
Film (50 μm of thickness).
Using the polarizer [I] with adhesive phase and the polarizer [II] with adhesive phase, conduct the following evaluation.
(re-workability)
Polarizer [I] obtained in will be above-mentioned with adhesive phase is cut into wide 25mm, release sheet is removed, by adhesive
Level, which is pressed into alkali-free glass, (Corning Incorporated's system " EAGLE XG ": thickness 1.1mm), to be made its stickup with 2kg roller, carries out autoclave
After handling (0.5MPa × 50 DEG C × 20 minute), 1 day, 20 days, 50 days are stood in the environment of 23 DEG C × 50%RH, later, are surveyed
It is fixed with 180 ° of peel angle, 300mm/ minutes peeling rates are removed when bonding force, evaluated with following benchmark.
(evaluation criteria)
After 1 day
A5N/25mm or less
B ultrasound crosses 5N/25mm and 10N/25mm or less
C is more than 10N/25mm or generation residue glue or substrate fracture
After 20 days
A5N/25mm or less
B ultrasound crosses 5N/25mm and 10N/25mm or less
C is more than 10N/25mm and 15N/25mm or less
D is more than 15N/25mm and 20N/25mm or less
E is more than 20N/25mm or generation residue glue or substrate fracture
After 50 days
A5N/25mm or less
B ultrasound crosses 5N/25mm and 10N/25mm or less
C is more than 10N/25mm and 15N/25mm or less
D is more than 15N/25mm and 20N/25mm or less
E is more than 20N/25mm or generation residue glue or substrate fracture
(durability)
Polarizer [I] and [II] by gained with adhesive phase are cut into 20cm × 15cm, and release sheet is removed, will be bonded
Oxidant layer face be pressed into alkali-free glass (Corning Incorporated's system " EAGLE XG ": thickness 1.1mm), pasted with reciprocal 2 times of 2kg roller it is viscous after,
It carries out autoclave process (0.5MPa × 50 DEG C × 20 minute), makes the sample of initial endurance test.
For gained sample, the polarizer after condition for being exposed to (1) heat resistance (80 DEG C × 500 hours) is carried out
Evaluation below.
(evaluation criteria)
Zero has no that foaming or end have no and floats in the entire surface of polarizer
× float in the visible foaming of entire surface of polarizer or end is visible
(wet-heat resisting albefaction)
Polarizer [II] by gained with adhesive phase is cut into 3.5cm × 3.5cm, release sheet is removed, by adhesive
Level be pressed into alkali-free glass (Corning Incorporated's system " EAGLE XG ": thickness 1.1mm), after being pasted with reciprocal 2 times of 2kg roller, into
Horizontal high voltage kettle handles (0.5MPa × 50 DEG C × 20 minute), makes the sample of wet-heat resisting albefaction test.
Gained sample is taken out, placed at room temperature in the environment of 60 DEG C × 90%RH after exposure 250 hours.So
Afterwards, the mist degree after measurement is taken out after 3 hours, evaluates wet-heat resisting albefaction.It should be noted that mist degree is to subtract conduct
It is worth obtained from the 1.1mm alkali-free glass value of blank.
(evaluation criteria)
Mist degree after just taking out
◎ is lower than 1%
0 1% more than or lower than 3%
△ 3% is more than or lower than 4%
× 4% or more
Mist degree after taking out 3 hours
◎ is lower than 1%
0 1% more than or lower than 2%
△ 2% is more than or lower than 3%
× 3% or more
(gel fraction)
The release sheet of polarizer (I) by gained with adhesive phase is removed, and from adhesive level picking adhesive, uses SUS
After the 200 mesh metal meshes cladding of system, it is immersed in the ethyl acetate for be adjusted to 23 DEG C 24 hours, will remains in metal mesh not
The weight percent of the adhesive ingredients of dissolution is as gel fraction.
(antistatic property)
< sheet resistance value >
After the above-mentioned polarizer (I) with adhesive phase is stood 24 hours under the atmosphere of 23 DEG C × 50%RH, remove viscous
The release sheet of mixture layer, with surface resistivity measurement device (Mitsubishi Chemical's ANALYTECH corporation, device name " Hiresta-UP
MCP-HT450 "), measure the surface resistivity of adhesive phase.
[table 3]
It from the above results, include the acrylic resin for being more than common polar functionalities monomer using by using
(A) it is obtained with alkoxy group content for the acrylic pressure-sensitive adhesive compositions of 15 weight % oligomeric silane coupling agent (B1) below
To adhesive embodiment 1~12 in, long-term re-workability and wet-heat resisting albefaction are excellent.
On the other hand it is found that utilizing acrylic resin (A ' -1, A '-for being free of more polar functionalities monomer by using
2) comparison for the adhesive that the acrylic pressure-sensitive adhesive compositions of the silane coupling agent with alcoxyl base unit weight greater than 15 weight % obtain
In example 1,2, long-term re-workability is excellent, but wet-heat resisting albefaction is poor.
It in addition we know, include the acrylic resin (A) and alkane for being more than common polar functionalities monomer using by using
The comparative example 3~9 for the adhesive that the acrylic pressure-sensitive adhesive compositions of silane coupling agent of the oxygroup amount greater than 15 weight % obtain
In, wet-heat resisting albefaction is excellent, but long-term re-workability is poor.
Silane coupling agent is hydrolyzed due to the moisture in adhesive system, is bonded by silanol group with glass surface, thus
Improve adaptation.It include to be easy intake in the acrylic resin of more polar monomer with the good degree of wet-heat resisting albefaction
Moisture in environment is easy to be influenced by hydrolyzing.Therefore, compared with usually, have the tendency that long-term re-workability reduces.It uses
In comparative example 1 and 2 without the acrylic resin compared with multiple polar group monomer, it is known that, even if being greater than using alkoxy group content
The silane coupling agent of 15 weight %, long-term re-workability will not become project.On the other hand, in embodiment 1~12, it is known that,
In the case where using with acrylic resin of the good degree of wet-heat resisting albefaction comprising more polar monomer, alkoxy is used
Content is 15 weight % oligomeric silane coupling agent (B1) below, and therefore, long-term re-workability, durability are also excellent.
In addition, adhesive obtained from being crosslinked using the acrylic pressure-sensitive adhesive compositions of above-described embodiment 1~12, is made partially
Tabula rasa is bonded with liquid crystal cells and makes image display device, as a result can precisely make gained image display device, resistance to
Long property is also excellent.
In above-described embodiment, the concrete mode in the present invention is shown, but above-described embodiment only simple example,
Being not construed as limiting property is explained.It will be apparent to those skilled in the art that various modifications be intended within the scope of the invention.
Industrial availability
For acrylic pressure-sensitive adhesive compositions of the invention, when manufacturing liquid crystal display device, as polarizer (protection
Film) with adhesive used in the stickup of liquid crystal cells (glass) in use, it is available after embody for a long time it is excellent again
Processability and even if use moisture-proof in the case where the polarizer using low polarity film as cyclic olefine film as protective film
Hot albefaction also excellent adhesive, as sticker displays, the optical component for constituting it optical component adhesive,
It is especially useful for pasting the polarizer of glass substrate of polarizer and liquid crystal cells etc. with adhesive.
Claims (9)
1. a kind of acrylic pressure-sensitive adhesive compositions, which is characterized in that contain:
Acrylic resin (A)；With, in the structure respectively containing 1 or more reactive functional groups and alkoxy silane it is even
Join agent (B),
The acrylic resin (A) is comprising from least 1 in hydroxyl monomer, carboxyl group-containing monomer, nitrogen containing monomer
The acrylic resin of 5~50 weight % of structural unit of kind polar functionalities monomer (a1),
The silane coupling agent (B) is 15 weight % oligomeric silane coupling agent (B1) below containing alkoxy group content.
2. acrylic pressure-sensitive adhesive compositions according to claim 1, which is characterized in that the oligomeric is silane coupled
The reactive functional groups equivalent of agent (B1) is 1600g/mol or less.
3. acrylic pressure-sensitive adhesive compositions according to claim 1 or 2, which is characterized in that the oligomeric silane
The weight average molecular weight of coupling agent (B1) is 3000 or more.
4. acrylic pressure-sensitive adhesive compositions described in any one of claim 1 to 3, which is characterized in that described to contain pole
Property group monomer (a1) at least contains carboxylic monomer.
5. acrylic pressure-sensitive adhesive compositions according to any one of claims 1 to 4, which is characterized in that further contain
Crosslinking dose (C).
6. acrylic resin composition according to any one of claims 1 to 5, which is characterized in that further contain
Antistatic agent (D).
7. a kind of adhesive, which is characterized in that it is acrylic adhesives combination according to any one of claims 1 to 6
Made of object is crosslinked by crosslinking agent (C).
8. a kind of polarizer adhesive, which is characterized in that it is using made of adhesive as claimed in claim 7.
9. a kind of image display device, which is characterized in that it is with adhesive as claimed in claim 7 by polarizer and liquid crystal list
Made of member is pasted.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2016-160171 | 2016-08-17 | ||
| JP2016160171 | 2016-08-17 | ||
| JP2016184538 | 2016-09-21 | ||
| JP2016-184538 | 2016-09-21 | ||
| PCT/JP2017/029083 WO2018034232A1 (en) | 2016-08-17 | 2017-08-10 | Acrylic adhesive composition, adhesive obtained using same, polarizing plate adhesive, and image display device |
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| Publication Number | Publication Date |
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| CN109476971A true CN109476971A (en) | 2019-03-15 |
| CN109476971B CN109476971B (en) | 2020-11-17 |
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| CN201780045281.4A Active CN109476971B (en) | 2016-08-17 | 2017-08-10 | Acrylic adhesive composition, and adhesive, adhesive for polarizing plate, and image display device each using same |
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| JP (2) | JP6977562B2 (en) |
| KR (1) | KR102358555B1 (en) |
| CN (1) | CN109476971B (en) |
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| WO (1) | WO2018034232A1 (en) |
Cited By (2)
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|---|---|---|---|---|
| CN115657178A (en) * | 2022-12-28 | 2023-01-31 | 深圳市全正科技有限公司 | Cold-curing laminating reflective film, preparation method thereof and optical display device |
| CN116041612A (en) * | 2022-12-30 | 2023-05-02 | 江苏斯迪克新材料科技股份有限公司 | Acrylate copolymer virgin rubber, pressure-sensitive adhesive and preparation method thereof |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018076489A (en) * | 2016-11-01 | 2018-05-17 | 日本合成化学工業株式会社 | Adhesive composition for polarizing plate, adhesive for polarizing plate, and polarizing plate with adhesive layer |
| JP2020145392A (en) * | 2019-03-08 | 2020-09-10 | 日東電工株式会社 | Dicing tape and dicing tape with adhesive film |
| KR102424024B1 (en) * | 2019-10-02 | 2022-07-25 | 주식회사 케이씨씨 | Primer composition for glass adhesive |
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- 2017-08-10 WO PCT/JP2017/029083 patent/WO2018034232A1/en active Application Filing
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Also Published As
| Publication number | Publication date |
|---|---|
| KR102358555B1 (en) | 2022-02-04 |
| TW201817840A (en) | 2018-05-16 |
| WO2018034232A1 (en) | 2018-02-22 |
| KR20190040190A (en) | 2019-04-17 |
| JP2021107564A (en) | 2021-07-29 |
| TWI731142B (en) | 2021-06-21 |
| JP6977562B2 (en) | 2021-12-08 |
| JP7137159B2 (en) | 2022-09-14 |
| CN109476971B (en) | 2020-11-17 |
| JPWO2018034232A1 (en) | 2019-06-20 |
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